Petroleum and other hydrocarbon oils.



- 1,277,005. No Drawing. Original application filed January 13, 1910,Serial No. 537,858. Divided and this application on a as rice.

-HEBMAN WILLEM KNOTTENBELT, OF ST.-GILLES, BRUSSELS, BELGIUM.

PETROLEUM AND OTHER I-IYDROCARBON OILS.

Specification of Letters Patent.

Patented Sept.3,1918.

filed July 3, 1916. Serial No. 107,464.

same.

This invention has for its objects an improved treatment of petroleumand shale oils.

It is characterized by the fact, that certain heavy oil fractions,generally, considered as by-products of the production of illuminatingoil can be utilized in the production of lamp oils, by means of thesuccessive treatment of the said fractions with acompara tively highpercentage of sulfuric acid and with an aqueous solution of ammoniacontaining commercial litmus i. 6., the so-called litmus cubes for thepurpose of obtaining oils suitable (as regards flash point andviscoscity) for use in lamps, having a higher Abel flash point and, withregard to their specific gravities,-- a greater illuminating power thanthose generally used, and to completely or partially-deodorize,decolorize and purifysaid oil. The oil to be treated, Whether crude ornot, is preferably first submitted to fractional distillation. Thefractions generally distilling between 150 C.

and 200 0., having specific gravities from 0.770 to 0.795 at 15 C. andAbel flash points between 18 C. and 40 (3;, are used for making aturpentine substitute.-

The fractions having specific g ravities from 0.790 to 0.840 at 15 C.and Abel flash points between 40 C. and 100 C., generally distillingbetween 180 C. and 300 C.,

' are utilized for the production of an illuminating oil. The selectionof these fractions depends somewhat on the quantity of paraffin'bodiescontained in the oil or distillate under treatment. These substancesincrease in the final fractions of the distillation. So the finalportions of every paraffinous oil should be tested and the parafinremoved, if necessary, before submitting the aforesaid fractions to thesubsequent treatment. The specific gravity as well as the flash pointswill vary more or less with the varieties of oil treated.

For instance, when carrying out my process in accordance with thisinvention, I apply the same to say a crude commercial distillate ofBoryslav' petroleum. This distillate is separated by fractionaldistillation into the following proportions:

3 parts by volume of 0.7570 specific gravity at 15 C. v

24 parts by volume of 0.7760 to 0.7780 spe cific gravity at 15 C.

73 parts by volume of 0.8255 specific gravity at 15 0., the lastmentioned fraction .having an Abel flash point of C.

The third portion is the one to be princi pally considered in connectionwith this invention. The oil, constituting this portion, is submitted tothe following treatment.

The separation of the tarry bodies is effected in the ordinary manner byagitating With sulfuric acid of 160 Baum (specific gravity 1.840).

ployed variesaccording to circumstances and is generally larger for myprocess than in the processes usually employed, and preferablyapproximates to or exceeds 3% of the Weight of. the oil or fraction tobe treated therewith. After settling, the oil is decanted a-mixturecontaining about 1 part of litmus cubes, 1 part of aqueous ammonia (28B. or 0.886 to 0.890 specific gravity, containing about 33% NH and 2parts of Water, (the parts are by weight). A larger quantity can beusedif necessary, as incase of treating a very impure oil fraction.After the incorporation of ammonia, litmus and. water with the oil beingtreated, agitation is carried on for half an hour and settling allowedfor several hours.

The oil is now separated by decantation.

The useof sulfuric'acid and of ammonia has already been recommended, butthe combined treatment with bothsubstances and litmus, unknown till nowin the industry of petroleum and other mineral oils, leads to a superiorfinal result.

The mixture containing ammonia and litmus is employed to effectdeodorization, de-

I coloration and clarification of the oil. The

.litmus in colloidal solution carries down certain heavy, greasy, finelydivided matters present in the oil in colloidal solution. The carbonateof lime, etc., in the litmus also aids in clarification of the oil, asit also carries down certain finely divided matters. The eflect of thelitmus is to decolorize and clarify the distillate, and to aid inremoving objectionable odors.

For the treatment of highly impure oil fractions, it is preferable todecant the alkaline solution of the'soluble constitutents of the litmuscubes, from the insoluble matter or sediment before adding the saidsolution to the oil which has been treated with acid.

-The ammonia is employed-to neutralize any acid remaining inthe oil,which acid exists therein as complex sulfo derivatives of hydrocarbons,and not as free acid; aminonia has the advantage over soda that it doesnot form substances as soda does that have a tendency to clog the wicks.

To the oil, now slightly yellow, is preferably added Floridas fullersearth, previ-' ously heated to a temperature of from 115 C. to 150 6.,to remove the yellow color..

After agitation and settling,the oil is decanted; i

'The burning oil, thus obtained, is substantially odorless; it burnswell, does not produce objectionable odors while burning, and has a'highilluminating power.

Although this invention is more particularly described with reference toa crude distillate of Boryslav petroleum, it will be understood that itis applicable to other varieties of petroleum or mineral oil with theresult that ultimate products of high commercial values are obtained.The treatment with an ammoniacal solution of litmus can be applied toany fraction of the distilled oil. l

The following examples of the treatment of other oils by the process ofmy invention, are given, to more fully illustrate the invention.

-A crude Burmah oil having a specific gravity of 0.815 at 15 C. and anAbel flash point of 20 Q, gave a fraction having a, gravity suitable forproducing illuminating 0% equal to 32% of theweight of the crude o1furic acid, ammoniacal solution of litmus and Floridas fullers"earthprocess, as above de-.

scribed, and gavea product having a specific gravity of 0.833 at 15 C.and an Abel flash point of 68 C.

A Scotch shale oil, called Twice run having 'a specific gravity of 0.815at 15 C. and an Abel flash point of 48 C. gave, by fractionation,burning oil fractions having specific gravities between 0.790 and 0.832at 15 C. and Abel flash points between 55 C.

This fraction was treated by the sillass, as above described. Roumania(schela tinte'a) crude 'oil and 100C. These fractions, being 64% of theinitial. bulk, were treated by the method above described, with 5% ofsulfuric acid of 66 Bauin (specific gravity 1.8 10) and then with theammoniacal solution of litmus, as above referred 'to.

A Sumatra crude oil having a specific gravity of 0.769 at 15 C. and anAbel flash point of 0 C., gave 36% of illuminating oil that when treatedby the sulfuric acid, am moniacal solution of litmus and fullers earthprocess, as above described, had a specific gravity of 0.800 at 15C. andan Abel flash point of 48 C.

A Borneo crude oil having a specific gravity of 0.879 at15 C. and anAbel flash point of 70 C., gave 6% of an illuminating oil fractionhaving a specific gravity of 0.842

at 15 C. and an Abel flash point of 27 (1., and also gave 14% of asecond illuminating oil fraction having a specific gravity of 0.882at'15 C., and an Abel flash point of 75 C., both of these fractionshaving been treated by the sulfuric acid, ammoniacal solution of litmus,and fullers earth process.

.A Galicia crude oil having a specific gravity of 0.828 at 15 (1., andan Abel flash point of 22 C., gave 10% of a first illuminating oilfraction having a specific gravity of 0.835 at 15 C. and an Abel flashpoint of 60 (3., and-10% of an illuminating oil fraction having aspecific gravity of 0.872 at 15 C. and an Abel flash point of 85 (1.,when treated by my process, as above de scribed. V

A Galicia (Wielopol) crude oil having a specific gravity of 0.8385 at 15C. and'an Abel flash point of 29 C. gave 15% of an illuminating oilfraction, having a specific gravity of 0.828 and an Abel flash point of60 0. and 4% of an illuminating oil frac tion having a specific gravityof 0.865 at-15 0., and an Abel flash point of 0. when treated by myprocess, as above described.

A Galicia (petrolea) crude oil having a specific gravity of 0.814: at.15C. and an Abel flash point of 18 .C., gave 15% of an illuminating oilfraction having a specific gravity of 0.812 at 15 C. with an Abel flashpoint of 52 (1., when treated by my process, as above described.

A Galicia (kabylanka) crude oil having a specific gravity of 0.835 at 15and'an Abel flash point of 26 C. gave 30% of an.

illuminating oil fraction having a specific gravity of 0.849 at 15 C.and an Abel flash point of 74 (1., when treated having a specificgravity of 0.897 at 15 C.

and an Abel flash point of 36 C gave 15%.

of an illuminating oil fraction having a "specific gravity of 0.825at.15 C. and an Abel fiash point of 70 0., and-5% of illuminating oilhaving a specific. gravity by my procof 0.868 at C. and an Abel flashpoint of 8891]. when treated by my process, above described. I

ABouman'ia crude-oil (buz eu') having a specific gravity of'0.8085 at 15C; and an described.

. A Hanover crude oil (wietze-steinfurej' havingfa'specifik: gravity of0.951 at 15 G.

' and an Abel flash point of 100? C. gave 26% of an illuminating. oilhaving a specific gravity of 0.870 at 15 C. and an Abel flash point of89 (3., when-treated by my proo ess, asabove described. In all thesecases, the: illuminatingoils,

after treatment bymy process, were of a superior character with regardto appear.-

. ance,-color, odor, combustibility and illuminating power.

Moreover the products produced were safety,.0ils, as proved by theflash-points,

which were much higher than those of many of the illuminating oils,consisting of petroleum fractions, now'on-the market.

The. present application is a division of my copending applicationSerial No. 537,858, filed Jan. 13, 1910, (which has now matured, intoPatent N0.'1,19.4,033, Aug. 8, 1916). c. \Vhat I claim is: 1. Theimproved process of treating petroleum and shale oils consistingin thetreatment of fractions having a specific "gravity of 0.790 to 0.840 andAbel flash The process of points between 40 C. and 100 C., distill ingat temperatures betweenabout 180 40.1

and about 300, C., with sulfuric acid and after that .with an aqueoussolution of ammonia and litmus 'substantiallyas and for the purpose setforth. treating oil distillates,

' l/Vitnesses:

. 3. The process ofj'treating, oil distillates which comprises acting]thereon with sul-I furicacid, and thereafter with ammonia and litmus. Pv 4. The process of treatingoildistillates, which comprises actingthereon with an acid, and thereafter: with ammonia and lit- -musfandfinallytreating with fullers earth.

5-. The process of. treating oil distillates, 'which comprises actingthereon with sulfuric acid, and thereafter ammonia andlitmus, andfinally treating with fullers earth.

'6. In the treatment of acid-treated hydrocarbonoils the step oftreating the same with an ammoniacal solution of litmus.

7 A-p1;ocess of treating an oil distillate I having a specific gravityof about 0.8255 which comprises treating with strong sulfuric acid inamount equal to about 3% of the weight of the distillate, and thereaftertreating with. an aqueous solution of ammonia and litmus each in amountequal to at least about 0.1% of the weight of the distillate. i L

8. A process of treating an oil distillate having a specific gravity ofabout 08255 which comprises treating with strong sul-. furic acid inamount equal togab'out3% of theweight of the distillate, and thereaftertreating with an aqueous solution Of'amf monia and litmus each in amountequal to signature in the presence of two witnesses.

HERMAN WILLEM KNOTTENBELT.

EDOUARD HARZEN, E. MEYER.

